Process for dyeing and printing polyester textile materials with 2-arylsulfonyl anthraquinone dyestuffs



United, States Patent;

PROCESS FOR DYEING AND PRINTING -POI.Y-

ESTER TEXTILE MATERIALS WITH Z-ARYL- SULFONYL, ANTHRAQUINONE DYESTUFFS Riitger Neeif, Wilhelm *Gohrbandt, Leverkusen, and Robert Kuth, Cologne- Muengersdorf, Germany, as: signors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Mar. 30, 1965, Ser. No. 444,053

Claims priority,'application Germany, Apr. 3, 1964,

F 42, 08 f v Int. Cl. D06p 1/20 U.S. Cl. 8-39 6 Claims ABSTRACT OF THE. DISCLOSURE Polyester materials are dyed andv printed with a'1,4- diamino-2-phenylsulfonyl-anthraquinone or -chl orophen ylsulfonyl-anthraquinone dyestuff by the thermosol process. The polyester materials may be polyethylene glycol terephthalate or cellulose triacetate materials and the resulting products which have fastness to light, 'wash ing, thermo-fixing and ironing.

The present invention is concerned with new a'nthra quinone dyestuffs which are suitable for dyeing and printing polyester materials by the thermosol process and is also concerned with the production of said new dyestuffs.

The new dyestuiis according to the present'inv'ention are compounds of the general formula I sozn l] l R: 0 R2 wherein R is selected from the group consisting of unsubstituted and substituted aryl, R is seletced from-the group consisting of hydrogen, halogen, cyano, unsub: stituted and substituted 'SR and SO R R .being selected from the group consisting of unsubstituted and substituted alkyl, aralkyl and aryl, R is'selected from the group consisting of hydrogen, hydroxyl, alkoxy,

amino, and NHSO aryl of which aryl can be substituted and R and R are each selected from the group consisting of hydrogen, nitro, amino and hydroxyl,-R and R not being OH when R is NH By the thermosolprocess thereis to beunders tood the process in which the printed or dyed'polyester mate v in v which the radicals Patented Dec. 30, 1969 :tain l6 carbon atoms, whereby the alkyl radical can again be further substituted, for example, by halogen atoms, or. hydroxy, alkoXYr ydroxyalkylenoxy, alkoxyalkylenoxy,= cyano or-carboxyalkyl groups or by amino groups optionally substitutedby alkyl, hydroxyl, alkoxyalkyl or ,cyanoalkyl radicals.

The compounds according to the present invention are obtained, for example, when compounds of the general formula:

4 B4 O ,NHz

' R1 1 1: fl' R3 0. R2

7 R, R R R and R have the same means as above, are oxidised in known manner, for example, with hydrogen peroxide. 7

The 'dyeings obtained on polyester materials with the new dyestufis according to the present invention possess very good drawingand' texture properties; the dyeings, which are obtained with very good dye yields, possess outstanding light, washing," thermo-fixing and ironing .fastnessesi The following exampleis given for the purpose of illustrating the present invention; the'parts and percentages being by weight unless otherwise indicated: 7 EXAMPLE (a) 'A' fabriciof polyethylene terephthalate fibres is impregnated on'a foulard with a dye bath which contains,

. per litre, 20 g. 1,4-diarnino Z-phenylsulphonyl-anthraquinone, as well as 10 g. of-a thermosol adjuvant, especially a polyether such as is described, for example, in Belgian patent 'sp'ecificationNof615,102. The fabric is then rials, optionally after an; intermediate drying,,are heated for a short time totemperaturesi-in-theregionof l80-'; 200 C. In general, the heating is carried out for a period of 30 secs. to 1.5 to 2 minutes. I

As polyester materials, there are particularly suitable the linear aromatic polyesters and, for example, .'cellulose esters, such as cellulose-triacetate..-

In the compounds according to the present invention,

the aryl radicals, which are preferably phenyl or naphthyl I radicals, can be substituted by one or more substituents of the most varied type. As examples, there can be mentioned the following substituents: halogen atoms, 'such as chlorine, bromine or fluorine atomsi-alkyl radicals containing 1-6 carbon atoms which, in turn, can be substituted by halogen atoms or hydroxyl, alkoxy, cyano or carboxyalkyl radicals; phenyl or phenoxy radicals, hydroxy radicals, alkoxy radicals containing 16.carbon atoms which again can be substituted by halogen atoms or hydroxyl, alkoxy, cyano or carboxyalkyl radicals; nonesterified and esterified carboxyl groups, trifluoromethyl,

squeezed to an increase in weight of and dried at -120? C.-in a moving jet drier or drying cupboard. Subsequently, the fabric is dried with hot air for about 45 seconds at 190200 C; in a tenter or nozzle hot flue,

' thereafter rinsed, optionally subjected to a reductive treatment, washed, rinsed and driedeThe reductive after-treatment for the purpose of removing dyestuff particles attached to the surfaces of the'fibres can be carried out by introducing the fabric at 259C. into a'bath containing 3-5 cc per litre .sodium hydroxyl solution (38 B.) and .1-2 g. per'litre concentrated sodium hydrosulphite solution, heated to 70 C. within a period of about 15 minutes-and maintained for a further 10 minutes at 70 C.

The fabric is subsequently hot rinsed, treated at 50 C.

with 2 3 cc. per litre: formic acid, rinsed and dried.

There is obtained a brilliant reddish-blue dyeing which is characterised by a high dyestuff yield and texture property, as well as by outstanding fastnesses, especially very good thermofixing and light fastnesses.

In a similar manner, a very full brilliant reddish-blue dyeing is obtained when, instead of the propylene ether fibres, cellulose triacetate fibres are used and the thermosol process carried out at 215 C.

Dyestufl Shade 93. 1-amino-2-(3-carbethoxy)-phenylsu1phonyl- Reddish-yellow anthraquinone.

94. 1-amin0-2-(2-ehloro-5-nitro) -phenylsulphonyl Do.

anthraquinone 95. 1-axnino-2-(4ethoxy)-phenylsulphonyl an- Do.

thraquinone.

96. 1-amino-2- (4 -B-hydr0xyethoxy) -phenylsul- D0.

phQnyLanthraquinOne.

97. 1-amino-2-(4-B-methoxyethoxy)-phenylsul- D0.

phonyl-anthraquinone. phonyl-anthraquinone.

98. l-arnino-Z-(4-fl-methoxy-B-ethoxyethoxy) D 0.

phenylsulphonyl-anthraquinone.

99. 1-amino-2-(4-phenoxy) -phenylsulphonyl- Do.

anthraquinone.

100 1-amino-2-(4-pheny1) -phenylsulphonyl Do.

anthraquinone.

101 1-amino-2- (4-B-cyanethoxy) -phenylsulph0nyl- D0.

anthraquinone.

102. 1-amin02-(4'-h ydroxy) -phenylsulphonyl- D o.

anthraquinone.

103 1-amino-2-(4-ethoxycarbonylmethyl)-phenyl- Do.

sulphonyl-anthraquinone.

(d) The production of the new dyestuffs according to the present invention is illustrated using, as an example, 1,4-diamino-Z-phenylsulphonyl-anthraquinone. The other compounds can be obtained in an analogous manner.

30 parts 1,4-diamino-2-phenylthio-anthraquinone in 500 glacial acetic acid are mixed at 40-45 C. with 34 parts 30% hydrogen peroxide, heated to 95 C. in about one hour and maintained at this temperature for 6-8 hours. After cooling, the resultant 1,4-diamino-2-phenylsulphonyl anthraquinone is filtered off with suction, washed with water and dried.

We claim:

1. A process for dyeing and printing polyester textile materials which comprises applying a 1,4-diamino-2- phenylsulfonylor chlorophenylsulfonyl-anthraquinone dystuif to such polyester textile materials by the thermosol process, said dyestulf having the formula:

wherein R is unsubstituted or substituted phenyl or naphthyl, R is hydrogen, halogen, cyano, unsubstituted or substituted -SR or SO R R being unsubstituted or substituted alkyl, aralkyl or aryl, R is hydrogen, hydroxyl, alkoxy, amino, or NH--SO ary1 of which aryl is unsubstituted or substituted and R and R are each hydrogen, nitro, amino or hydroxyl, R and R not being OH when R; is NH 2. A process according to claim 1, wherein the dyestulf is applied to polyethylene glycol terephthalate textile materials.

3. A process according to claim 1, wherein the dyestuff is applied to cellulose tn'acetate textile materials.

4. Polyester textile materials printed and dyed by the thermosol process of claim 1.

5. A process according to claim 1, wherein the dyestutf is a 1,4-diamin0-2-phenylsulfonyl-anthraquinone.

6. A process according to claim 1, wherein the dyestufi' is 1,4-diamino-2-(4'-chlorophenylsu1fonyl)-anthraqumone.

References Cited UNITED STATES PATENTS 2,870,172 1/1959 Schoenauer 8-39 X FOREIGN PATENTS 1,268,400 6/ 1961 France.

1,332,541 6/1963 France.

GEORGE F. LESMES, Primary Examiner T. J. HERBERT, JR., Assistant Examiner US. Cl. X.R. 

